Dyestuffs of the anthraquinone series



United States Patent :DYESTUFFS OF THE ANTHRAQUINONE SERIES Ernst Anton and Karl Saftien, Ludwigshafen (Rhin'e), Germany, assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft,iLudwigshafen (Rhine), Germany No Drawing. Application March 23, 1956 Serial No. 573,344

Claims priority, application 'G'ermanyMarch 24, 1955 :iG 'QIaims. (Cl. 260376) This invention yrelatesto dyestuflis of the :anthraquinone series, and more particularly .to dyestuffs of 'esterified monoand dicarboxylic acids of the anthraquinone series.

We have found that new and valuable dyestuffs of the :anthraquinoneseries can 'be obtained which have the gener al :forrnu la wherein Y is a member of the group consisting of amino, arylamino, and hydroxyl radicals, R is a member of the group consisting of alkyl and -.cycloalkyl 'radicalsconztainingnot anorethan 8 carbon:atom-s,.and n is t'anzinteger .;of .1 to 2. The carboxylicacid :ester group :is showniin 'hydroxyl group, or by other substituents capable offbe'ing converted into an amino or hydroxyl group by conventional methods either before or after esterification.

Suitable monoand di-carboxylic acids of the anthraquinone series are for example 1.4-diaminoanthraquinone- 2;3-dicarboxylic acid, l-arninoor 1-methylamino-4-n'itroanthraquinone-2-carboxylic.acid, l-arnino-4-brornoanthraquinone-Z-carboxylic acid, l.4-dibromoanthraquinone-2- carboxylic acid, 1.4-dichloroanthraquinone-6-carbQXylic acid, 1.4-dichloroanthraquinone-S-carboxy1ic acid or 1- amino-4-hydroxyanthraquinone-2-carboxylic acid.

Suitable esterification components are for example methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, hexyl alcohol, octyl alcohol, cyclohexanol, dimethyl cyclohexanol, benzyl alcohol or phenyl ethyl alcohol.

For the esterification it is preferable to heat the chlorides of the said carboxylic acids with-a large excess of the monohydroxyl compounds at about 60 to 110 C. Usually the esters separate in Well-crystallized form upon cooling. The carboxylic acids can however also be converted directly into their esters by heating with sulfuric acid esters of the alcohols, as for example with methyl or ethyl sulfuric acid.

When the resulting esters contain a nitro group in the 1- and/or 4-position of the anthraquinone nucleus, this is then reduced to the amino group by conventional methods, as for .example with stannous chloride and :hydrochloric acid or with alkali hyposulfite. .If halogen atoms are present in the alpha-positions of the anthraquinone nucleus, these are also reacted by conventional methods with arylamines, such as aniline, or with sulv-fonamides, such as toluene sulfonamide, the ,sulfonyl group then being split off by hydrolysis.

Patented Feb. 11, 1958 ice The :new compounds are in general formed in very good yields and excellent purity. They are hardly soluble in water but dissolve in most organic solvents with clear .bluearedto blue colors. They may therefore serve with advantage for coloring these solvents, as for example ,lhydrocarbons. In particular, however, :they are distinguished by .an excellent dyeing value for fibres of polyester fibres as for example polyterephthalic acid glycol ester on which they yield clear violet to blue .dyein'gs of very good fastness. They are also suitable for dyeing fibres of polyamides and polyurethanes as well as :of cellulose esters or ethers, on which they have a remarkable fastness to waste gas.

The dyeing of the fibres, "threads, yarns, fabrics or webs can be effected for example by treating them in an ,aquepnsrlyebath containing the dyestuffs in finely divided torm, zat elevated temperature, preferably at the rboiling temperature of 'water. The .dyebath may also .have added thereto soaps or :other dispersing or wetting ,agents. 4 a The followinggcxarnples will-further illustrate this :in- ,vention 'but .the invention ,is not restricted to these exam- ,ples. ;lihe,parts,are,parts by weight.

Example 1 10 parts of '1amino-4-riitroanthraquinone-2-carboxylic acid chloride and 100 parts ofacyclohexanol are heated at 110 to 120 C. until ,the evolution of hydrochloric acid is completed. Upon cooling, l-aniinol-nitroanthraquinone-Z-carboxylic aciid cyclohexyl ester crystallizes out. It is filtered off by suction, washed with cyclohexanol and alcohol and dried.

5.9 parts of this ester are suspended in 30 parts of alcohol and there is added thereto a solution of 14 parts vof stannouschloridein 14 parts .of concentrated hydro- .chloric acid. Thetemperature thereby rises :to about 60 (3.. his then boiled for a short time, cooled, ,filtered by :suctionand ,the gdarkfred crystals vsuspended in 150-parts of water at: 60 .to 10 C. and a powerful current of air led through ,the ,liquid. In :this way a change ,of color to blue takes place. The precipitate .is .filtered ofi' by suction, .washed thoroughly with water, .dried and re crystallized fromdioxane. Thedyestulfhas the formula:

5 NHz and colors hyd-rocar'bons clear blue shades.

Example .2

'10 parts of lFamino-41nitroanthraquinone-2-carboxylic acid chloride and ,50 parts of isobutyl alcohol are :boiled for-2.;hours under reflux. After cooling, the ester formed is filtered zoif'by suction, washed with isqpropyl alcohol and methanol and then reduced at to ,C. with a solution of 14 parts of sodium hyposulfite in 240 parts of water. A powerful current of air is led through the reaction mixture, the blue precipitate which separates is filtered off by suction, washed with water until neutral and recrystallized from dioxane containing water. The dyestuff yields clear blue dyeings of excellent fastness to light and washing on polyterephthalic acid glycol ester, 4 polyamide and acetate rayon fibres. According to analysis, 1.4-diaminoanthraquinone-Z-carboxylic acid isobutyl ester is present, having the formula:

l CH;

C O OCHr-C Example 4 10 parts of 1-amino-4-nitroanthraquinone-2-carboxylic acid chloride and 100 parts of ethanol are boiled for some hours. The ethyl ester formed is filtered off by suction, after cooling, and washed with alcohol. It can be converted in the way described in Example 1 or 2 into 1.4- cliaminoanthraquinone-Z-carboxylic acid ethyl ester. The dyestuff is purified by recrystallization from a mixture of dioxane and water. It dyes polyterephthalic acid glycol. ester and polyamide fibres brilliant blue shades of good fastness properties. The dyestuff has the formula:

C O 0 (M O NH,

Example 5 10 parts of 1-amino-4-bromoanthraquinone-Z-carboxylic acid chloride and 70 parts of cyclohexanol are heated at 110 C. for 2 hours. The mixture is then cooled, 1 amino 4 bromoanthraquinone-2-carboxylic acid cyclohexyl ester thereby separating in red-brown crystals. It is filtered off by suction, washed with cyclohexanol and alcohol and dried.

9.5 parts of the ester thus obtained are boiled with 6 parts of para-toluenesulfonamide, 4 parts of potassiumacetate, 0.2 part of copper powder, 0.2 part of copper acetate and parts of butanol until the solution has become free from halogen. By adding methanol, violet crystals separate. These are filtered off by suction, washed with butanol and alcohol, dried and then dissolved in 3 parts of 90% sulfuric acid. After stirring for an hour at normal temperature it is poured onto ice and then the sulfuric acid is neutralized by the addition of sodium 5 carbonate. The deposited blue precipitate is filtered ofi by suction, washed neutral with water and dried. The dyestutf can be purified by recrystallization from dioxane.

It is identical with the product obtainable according to Example 1.

Example 6 25 parts of 1.4-dichloroanthraquinone-G-carboxylic acid chloride and 150 parts of ethanol are boiled under reflux for 3 hours. After cooling it is filtered by suction, washed with ethanol and dried.

21 parts of the yellow 1.4-dichloroanthraquinone-6- carboxylic acid ethyl ester thus obtained are heated for 6 hours at 170 C. with 33 parts of para-toluenesulfon acetate and 150 parts of nitrobenzene. The reaction mixture thus becomes colored intense red. It is allowed to cool and is filtered off by suction, washed with nitrobenzene, alcohol and water and dried. The brilliant red crystals of l.4-bis(para-toluenesulfonamino)-anthraqni- :ness from aqueous dispersion.

' none-6-carboxylic acid ethyl ester are dissolved in 250 r lowing formula:

(II) NH Example 7 By replacing the 1.4-dichloroanthraquinone-G-carboxylic acid in Example 5 by the same amount'of 1.4-dichloroanthraquinone-S-carboxylic acid, there is obtained the dyestufi of the following formula:

(f NH;

| HsCnOOC O N 2 It is a blue-red powder which dyes polyamide, acetate rayon and polyterephthalic acid glycol ester fibres brilliant violet shades of good fastness from aqueous dispersion.

Example 8 dried.

hours at C. with 56 parts of aniline, 13.6 parts of 23 parts of the 1-amino-4-bromoanthraquinone-Z-carboxylic acid ethyl ester thus obtained are heated for 7 potassium acetate and 0.1 part of copper acetate, the

original red color of the mixture thereby changing to bluegreen. 100 parts of methanol are stirred in, the separated crystals are filtered off by suction, washed with greenish-blue needles and has the following formula:.

(I? NH,

GOOCaHs It dissolves in organic solvents with a blue-green color and dyes polyterephthalic acid glycol ester, polyamide and acetate rayon fibres clear greenish-blue shades of good amide, 24 parts of potassium acetate, 0.5 part of copper 70 fastness from aqueous dispersion.

Example 9 10 parts of l,4-diaminoanthraquinone-2.3-dicarboxylic acid and 100 parts of methyl sulfuric acid are heated at C. until a sample withdrawn in no longer soluble (I) NH:

COOCHt COOCH:

| O NH:

It dyes polyterephthalic acid glycol ester, polyamide and acetate rayon fibres clear blue shades of excellent fastness.

If the methyl sulfuric acid be replaced by the same amount of ethyl sulfuric acid, then by heating at 100 C. 1.4-diaminoanthraquinone-2.3-dicarboxylic acid diethyl ester is obtained which yields also clear blue shades of similar fastness on polyterephthalic acid glycol ester, polyamide and acetate rayon fibres.

Example 30 parts of l-amino-4-hydroxyanthraquinOne-Z-carboxylic acid and 200 parts of methyl sulfuric acid are heated for 30 minutes at 140 C. After cooling, it is poured into ice-water and the deposited blue-red precipitate is filtered off by suction, washed with water until neutral and dried. By recrystallization from dioxane the new dyestuff is obtained in the form of violet needles. It has the formula:

COOCH:

0 H and dyes polyterephthalic acid glycol ester, polyamide and acetate rayon fibres violet shades of good fastness.

What we claim is: 1. A dyestuif of the anthraquinone series having the general formula (f NH;

O il-OR).

wherein Y is a member of the group consisting of amino, phenylamino, and hydroxyl radicals, R is a member of the group consisting of saturated alkyl and cycloalkyl radicals containing not more than 8 carbon atoms, and n is an integer of 1 to 2.

2. A dyestutf having the formula I 0 NH, 3. A dyestuff having the formula O NH: 4. A dyestuff having the formula O NH:

5. A dyestufl having the formula 6. A dyestutf of the anthraquinone series having the general formula O NH:

wherein Y is a member of the group consisting of amino, phenylamino, and hydroxy radicals and R is a member of the group consisting of saturated alkyl and cycloalkyl radicals containing not more than 8 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS 1,849,444 Wilke Mar. 15, 1932 FOREIGN PATENTS 661,045 Great Britain Nov. 14, 1951 

1. A DYESTUFF OF THE ANTHRAQUINONE SERIES HAVING THE GENERAL FORMULA 